JP3665345B2 - Adsorbents for phosphates from aqueous media, their manufacture and use - Google Patents
Adsorbents for phosphates from aqueous media, their manufacture and use Download PDFInfo
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Description
本発明は、水性媒質からの、例えば水溶液からのリン酸塩(Phosphate)に対する吸着剤に関するものである。それは特に、無機リン酸塩および食品に結合したリン酸塩に対する吸着剤として、とりわけ高リン酸血症状態の予防および治療に経口的に適用する製剤として適している。
慢性腎不全の患者において、病理学的に増加した血清リン酸塩レベルは、糸球体濾過率の減少によって起こる。それによって起こる二次的な副甲状腺機能亢進症は、腎性オステオパシーの発症の原因の一つとしてみなさなければならない。普通、透析によってまたは胃腸管における食品リン酸塩の吸収を抑制する経口的リン酸塩吸着剤の投与によってまたはこれらの両方法の組み合わせによって、リン酸塩バランスを平衡に維持する試みがなされている。しかしながら、現在の技術の状態においては、これは十分に有効でなく、経済的でなく、または副作用に悩まされる。
すなわち、透析脳障害症候群のほかに、経口的リン酸塩吸着剤として使用されるアルミニウム(III)塩は、腎性オステオパシーおよび小球性貧血を起こす。カルシウム塩を使用する場合は、しばしば、血管および内部器官の石灰化および胃腸病と組み合わされた高カルシウム血症が起こる〔Dialysis Journal 37, 1-40(1991)〕。
さらに、多核性金属オキシドヒドロキシドで変性した吸着物質の使用が、DE 42 39 442 A1において提案されているが、その中に記載されている水溶性鉄デキストランおよびデキストリンの使用は、これらが吸収性であるという不利点を有している。小量の鉄のみを放出する複合体は、交叉結合した多糖類担体の使用によって製造することができる。アルファー鉄水酸化物を基にしたこれらの複合体の不利点は、第一に使用される交叉結合した多糖類担体の費用が高いことでありそして第二に改善を必要とするリン酸塩吸着能力である。
それ故に、本発明の目的は、水性媒質からの、特に水溶液からのリン酸塩に対する吸着剤を提供することである。特に、吸着剤は体液、びじゅくおよび食品からの無機リン酸塩および食品に結合したリン酸塩に適しているものでなければならず、吸着剤は改善されたリン酸塩吸着能力を示さなければならずそして吸着剤は、簡単に且つ経済的に製造することのできるものでなければならない。
この目的は、炭水化物によっておよび(または)フミン酸によって安定化された多核性ベータ−鉄水酸化物を含有する、本発明が第一に関係する水性媒質からのリン酸塩に対する吸着剤によって達成することができるということが示された。これらの吸着剤は、特に例えば無機リン酸塩および食品に結合したリン酸塩を吸着するための水溶液からのリン酸塩の吸着に適している。
本発明の範囲内において、多核性ベータ−鉄水酸化物は、すぐれたリン酸塩吸着能力を有しているということが示された。しかしながら、多核性ベータ−鉄水酸化物は時間の経過につれて構造が変化するので、それはこれまでこの目的に使用することができなかった。本発明の範囲内において、安定化は、適当な化合物、特に炭水化物およびフミン酸によって行うことができるということが見出された。しかしながら、何れかの一つの理論に拘束されることなく、炭水化物との複合体形成は起こらないものと考えられる。
さらに本発明は、無機リン酸塩および食品に結合したリン酸塩に対する吸着剤としてまたは吸着剤中に使用することのできる、炭水化物によっておよび(または)フミン酸によって安定化された多核性ベータ−鉄水酸化物を製造する方法に関するものである。本発明による方法においては、塩基の水溶液を、クロライドイオンを含有する鉄(III)塩の水溶液と混合して3より高いpH、例えば3〜10のpHを有する褐色のベータ−鉄水酸化物の懸濁液を形成させる。次に、この懸濁液をよどませる。実際には、懸濁液を例えば1〜5時間放置することができる。それをこの段階において適宜軽く撹拌することができる。例えば、それを10分の間隔で軽く(例えば10分)撹拌することができる。得られたベータ−鉄水酸化物を水で洗浄する。これは例えば、傾瀉分離、濾過および(または)遠心分離によって行うことができる。洗浄は妨害する陰イオン、例えばクロライドイオンが除去されるまで実施する。湿った生成物が得られる。この湿った生成物は乾燥していない。この湿った生成物を、水中でスラリー化する。水の量は重要でない。使用される操作は、好ましくは得られた懸濁液の鉄含有量(Feとして計算した)が6重量%まで、最も好ましくは2〜6重量%であるように行われる。
例えば、水溶液中の炭酸ナトリウムまたは重炭酸ナトリウムを、アルカリ金属の炭酸塩またはアルカリ金属の重炭酸塩の溶液として使用することができる。
例えば、無機酸または有機酸の水溶性塩を、鉄(III)塩として使用することができる。塩化鉄(III)が好ましい。
β−鉄水酸化物(アカガナイト)の製造は、原則的に従来の技術において既知でありそして文献、例えばU. SchwertmannおよびR.M. Cornell, “Iron Oxides in the Laboratory", VCH Verlagsgesellschaft mbH, 1991, 95-100に記載されている。経済的理由によって、β−鉄水酸化物を含有する吸着剤を工業的に製造するために、高いpH値において定量的に鉄を沈澱させることが必要である。上述した文献の100頁に記載されているように、フエリハイドライトもまた同時に沈澱する。これらのようなβ−鉄水酸化物およびクエリハイドライトの混合物もまた、本発明による吸着剤として使用することもできそしてそれ故に、本発明はまたこれらの化合物に関するものである。
1種または2種以上の炭水化物および(または)フミン酸を、上述したようにして得られた懸濁液に加える。好ましくは、水溶性化合物が使用される。炭水化物および(または)フミン酸は、固体の形態において添加することができる。この場合において、これらの物質は存在する水に溶解することができる。しかしながら、炭水化物の水溶液を添加することもできる。
炭水化物またはフミン酸の量は、好ましくは鉄(Feとして計算)1g当たり炭水化物またはフミン酸少なくとも0.5gを加えるように選択される。最大の鉄含有量は、40重量%でなければならない。炭水化物および(または)フミン酸の最大の含有量については何ら制限はなくそして主に経済的理由によって決定される。
特に種々の糖、例えばアガロース、デキストラン、デキストリン、デキストラン誘導体、セルロースおよびセルロース誘導体、サッカロース、マルトース、ラクトースまたはマンニトールのような可溶性炭水化物を、炭水化物として使用することができる。
本発明によって製造される不溶性の安定化された多核性のベータ−鉄水酸化物を含有する吸着物質は、高いリン酸塩結合能力のほかに、これらの物質が鉄を殆ど放出することなく安く製造されるという利点を有している。
1種または2種以上のカルシウム塩を、本発明による吸着剤に加えることが有利でありそして好ましい。適当なカルシウム塩の例は、無機酸または有機酸の塩、特に酢酸カルシウムを包含する。リン酸塩結合能力は、特に高いpH値において、カルシウム塩の添加によって増加される。カルシウム塩を有するこれらの吸着剤のような吸着剤は、十分なリン酸塩結合能力が高いpHでもなお保持されるので、特に5より高いpH値において有利に使用することができる。
鉄1g当たりカルシウム塩、特に酢酸カルシウム400mg〜2g、例えば約1gの添加が、特に有利であるということが示された。
本発明による吸着剤は、例えば経口的適用のために処方することができる。これらの吸着剤は、それ自体でまたは慣用の薬剤添加剤、例えば慣用の担体または補助物質と一緒に処方することができる。例えば医薬分野において使用されている慣用の媒質を被包媒質として使用して被包を行うことができる。また吸着剤を場合によっては、補助物質および添加剤と一緒に、顆粒、錠剤、糖剤として提供するかまたはサッシェ剤中に含ませることもできる。本発明による吸着剤の一日当たりの用量は、例えば鉄1〜3g、好ましくは1.5gである。
本発明による吸着剤はまた、食品に結合したリン酸塩の吸着に使用するのに適している。この目的のために、例えば吸着剤を食品と混合する。この目的に対する処方は、例えば薬剤について上述したようにして製造することができる。
本発明を以下の実施例によってより詳細に説明する。
実施例 1
塩化鉄(III)溶液(d20=1.098g/ml)275gを、30分にわたって撹拌(ブレード撹拌器)しながら、ソーダ溶液(d20=1.185g/ml)241.5gに滴加した。懸濁液を2時間放置した。この時間の間、それを10分ずつ6回撹拌した。それから得られた懸濁液を撹拌しながら、水300mlで処理し、1時間放置し、上澄液を傾瀉分離によって除去した。この操作を5回反復した。
4.8%の鉄含有量(錯滴定的に測定)を有する懸濁液208.3gを得た。
サッカロース15gおよび澱粉15gを、上記懸濁液208.3gに加えた。それから懸濁液を、回転蒸発器中において50℃で濃縮しそして高真空下40℃で乾燥した。
21.2%の鉄含有量(錯滴定的に測定)を有する粉末47.2gを得た。
実施例 2
リン酸塩水溶液からの無機リン酸塩に対する実施例1により製造された物質の結合能力の測定
リン酸ナトリウム溶液(Na3PO4×12H2O 13.68g/L)10mlを、実施例1によって製造された物質236mg(鉄0.9ミリモルに相当する)に加えた(Fe:Pモル比=1:0.4)。pHを3.0、5.5または8.0に調節した後に、懸濁液を37℃で2時間反応させた。その後、懸濁液を遠心分離しそして上澄液を傾瀉分離によって除去した。試料を蒸溜水で25mlとしそしてそのリン含有量をリン−モリブデン試験によって測光的に測定した。
実施例 3
Na3PO4×12H2O 27.36g/Lを含有するリン酸ナトリウム溶液10mlを上述した物質236mgに添加する(Fe:Pモル比=1:0.8)以外は、実施例2と同様にして、リン酸塩水溶液からの無機リン酸塩に対する実施例1によって製造された物質の結合能力の測定を行った。
実施例 4
リン酸塩水溶液からの有機リン酸塩に対する実施例1によって製造された物質の結合能力の測定
グリセロリン酸塩溶液(グリセロリン酸ジナトリウム塩五水和物11.02g/L)10mlを、実施例1によって製造された物質236mg(鉄0.9ミリモルに相当する)に加えた(Fe:Pモル比=1:0.4)。pHを3.0、5.5または8.0に調節した後、懸濁液を37℃で2時間反応させた。その後、懸濁液を遠心分離しそして上澄液を傾瀉分離によって除去した。試料を蒸溜水で25mlにしそしてローレンツ試薬によって有機的に結合したリン酸塩を、消化させそして無機リン酸塩を沈澱させた後にリン含有量を重量分析的に測定した。
実施例 5
リン酸塩水溶液からの有機リン酸塩に対する実施例1によって製造された物質の結合能力の測定
フイチン酸溶液(フイチン酸23.4g/L)10mlを、実施例1によって製造された物質236mg(鉄0.9ミリモルに相当する)に加えた(Fe:Pモル比=1:0.4)。pHを3.0、5.5または8.0に調節した後、懸濁液を37℃で2時間反応させた。その後、懸濁液を遠心分離しそして上澄液を傾瀉によって除去した。試料を蒸溜水で25mlにしそしてローレンツ試薬によって有機的に結合したリン酸塩を消化させそして無機リン酸塩を沈澱させた後にそのリン含有量を重量分析的に測定した。
実施例 6
サッカロース30.0gを、実施例1によって製造された懸濁液208.3gに加えた。それから、懸濁液を回転蒸発器中において50℃で濃縮しそして高真空下40℃で乾燥した。得られた物質のリン酸塩結合能力を実施例2と同様に測定した。
実施例 7
アミロペクチン30.0gを、実施例1によって製造された懸濁液208.3gに加えた。それから懸濁液を、回転蒸発器中において50℃で濃縮しそして高真空下40℃で乾燥した。得られた物質のリン酸塩結合能力を、実施例2と同様に測定した。
実施例 8
白色デキストリン(アミルム、Blattmannにより供給された)30.0gを、実施例1によって製造された懸濁液208.3gに加えた。それから懸濁液を、回転蒸発器中において50℃で濃縮しそして高真空下40℃で乾燥した。得られた物質のリン酸塩結合能力を、実施例2と同様に測定した。
実施例 9
フミン酸(Fluka, Item No. 53860)30.0gを、実施例1によって製造された懸濁液208.3gに加えた。それから懸濁液を、回転蒸発器中において50℃で濃縮しそして高真空下40℃で乾燥した。得られた物質のリン酸塩結合能力を、実施例2と同様に測定した。
実施例 10
リン酸塩水溶液からの無機リン酸塩に対する商業的に入手できる酸化鉄(III)の結合能力の測定
リン酸ナトリウム溶液(Na3PO4×12H2O 13.68g/L)10mlを、鉄50mg(鉄0.9ミリモルに相当する)に相当する酸化鉄(III)の量に加えた(Fe:Pモル比=1:0.4)。pHを3.0、5.5または8.0に調節した後に、懸濁液を37℃で2時間反応させた。その後、懸濁液を遠心分離しそして上澄液を傾瀉分離によって除去した。試料を蒸溜水で25mlとしそしてそのリン含有量をリン−モリブデン試験によって測光的に測定した。
実施例 11
リン酸塩水溶液からの無機リン酸塩に対するα−、β−およびγ−鉄オキシ水酸化物の結合能力の測定。リン酸塩結合能力は、実施例10と同様に測定した。
実施例 12
リン酸塩水溶液からの無機リン酸塩に対する安定化されたα−、β−およびγ−鉄オキシ水酸化物の結合能力の測定。1:1.5:1.5の重量比のFe:サッカロース:澱粉において、サッカロースおよび澱粉を実施例11からのオキシ水酸化鉄に加えた。
リン酸塩結合能力を実施例10と同様に測定した。
実施例 13
リン酸塩水溶液からの無機リン酸塩に対する酢酸カルシウムと、実施例1によって製造された物質との混合物の結合能力の測定
酢酸カルシウム(含有量93.5〜94.5%)0.96gを、20.4%の鉄含有量を有する実施例1によって製造された物質5gに加えそして十分に混合した。得られた物質のリン酸塩結合能力を実施例2と同様に測定した。
実施例 15
実施例6によって製造された物質を、水で懸濁液とし、30分撹拌し、遠心分離しそして上部相を傾瀉分離によって除去した。糖が水性相においてもはや検出されなくなるまでこれを反復する。この方法において、洗浄操作後、使用されたサッカロースの1.8%が調製品中においてなお検出することができる。これは洗浄した物質において15:1のFe:サッカロースに相当する。これは糖が複合体として結合されていないということを示す。
実施例 16
0.8%の全リン含有量を有する標準ラットかいばを製造するために、乾燥した粉末の分離した成分を、激しく十分に混合した後にシリンダーに入れそして圧縮してペレットを得た。Weender分析によるかいばの組成は、以下の表に示した値に相当する。全体のリン含有量は、0.75%の有機的に結合したリン酸塩および0.05%無機リン酸塩として分配した。
この製造と平行して、同じ出発物質の第二のバッチを同じ処方によって製造した。このバッチはさらに追加的に、実施例1により製造された物質3w/w%を含有する。
製造の完了後および約2ケ月の貯蔵期間の後に、有効なリン酸塩に対する分析を、両方の食品のバッチについて遂行した。リン酸塩吸着剤を含有していない製剤からなる比較対照においては、使用した量の84.5%に相当する0.68%のリン酸塩含有量が見出された。試験製剤においては、使用した量の62.6%に相当する0.50%のリン酸塩含有量が見出された。
かいば1g当たりP 1.75mgに相当する21.9%の差は、3%の吸着剤含有量における吸着剤1g当たりP 1.9ミリモルの結合能力に相当する。
吸着剤を含有していない比較対照製剤に対するWeender食品分析の結果:
粗製タンパク質 19.7%
粗製脂肪 3.2%
粗製繊維 5.4%
粗製灰分 6.5%
水 10.9%
自由に注出できるN 54.3%
Ca含量 1.2%
P含量 0.8%
Kahlペレット硬度 17.3The present invention relates to an adsorbent for phosphate from an aqueous medium, for example from an aqueous solution. It is particularly suitable as an adsorbent for inorganic phosphate and food-bound phosphate, especially as a formulation applied orally to the prevention and treatment of hyperphosphatemia conditions.
In patients with chronic renal failure, pathologically increased serum phosphate levels are caused by a decrease in glomerular filtration rate. The resulting secondary hyperparathyroidism must be regarded as one of the causes of the development of renal osteopathy. Attempts have been made to maintain phosphate balance, usually by dialysis or by administration of an oral phosphate adsorbent that inhibits the absorption of food phosphate in the gastrointestinal tract, or by a combination of both of these methods. . However, in the state of the art, this is not effective enough, is not economical, or suffers from side effects.
That is, in addition to dialysis encephalopathy syndrome, aluminum (III) salt used as an oral phosphate adsorbent causes renal osteopathy and microcytic anemia. When calcium salts are used, hypercalcemia often occurs combined with calcification of the blood vessels and internal organs and gastrointestinal disease [Dialysis Journal 37 , 1-40 (1991)].
In addition, the use of adsorbents modified with polynuclear metal oxide hydroxides has been proposed in DE 42 39 442 A1, but the use of the water-soluble iron dextran and dextrin described therein is absorptive. Has the disadvantage of being. Complexes that release only small amounts of iron can be produced by the use of cross-linked polysaccharide carriers. The disadvantage of these complexes based on alpha iron hydroxide is that the cost of the cross-linked polysaccharide support used is first and secondly phosphate adsorption that needs improvement Is ability.
The object of the present invention is therefore to provide an adsorbent for phosphate from aqueous media, in particular from aqueous solutions. In particular, the adsorbent must be suitable for inorganic phosphate from body fluids, juices and foods and phosphates bound to foods, and the adsorbent must exhibit improved phosphate adsorption capacity. And the adsorbent must be one that can be produced easily and economically.
This object is achieved by an adsorbent for phosphate from an aqueous medium to which the present invention is primarily concerned, containing polynuclear beta-iron hydroxide stabilized by carbohydrates and / or by humic acid. It was shown that you can. These adsorbents are particularly suitable for the adsorption of phosphate from aqueous solutions, for example for adsorbing inorganic phosphate and phosphate bound to food.
Within the scope of the present invention, it has been shown that polynuclear beta-iron hydroxide has excellent phosphate adsorption capacity. However, since polynuclear beta-iron hydroxide changes in structure over time, it could not be used for this purpose until now. Within the scope of the present invention, it has been found that stabilization can be effected by suitable compounds, in particular carbohydrates and humic acids. However, without being bound by any one theory, it is believed that complex formation with carbohydrates does not occur.
The present invention further relates to polynuclear beta-iron stabilized by carbohydrates and / or by humic acid, which can be used as or in adsorbents for inorganic phosphate and phosphate bound to food. The present invention relates to a method for producing a hydroxide. In the process according to the invention, an aqueous solution of a base is mixed with an aqueous solution of an iron (III) salt containing chloride ions and a brown beta-iron hydroxide having a pH higher than 3, for example 3-10. A suspension is formed. The suspension is then allowed to stir. In practice, the suspension can be left, for example, for 1 to 5 hours. It can be stirred as appropriate at this stage. For example, it can be stirred lightly (eg 10 minutes) at 10 minute intervals. The resulting beta-iron hydroxide is washed with water. This can be done, for example, by decantation, filtration and / or centrifugation. Washing is performed until interfering anions, such as chloride ions, are removed. A wet product is obtained. This wet product is not dry. This wet product is slurried in water. The amount of water is not important. The operation used is preferably carried out in such a way that the iron content (calculated as Fe) of the suspension obtained is up to 6% by weight, most preferably 2-6% by weight.
For example, sodium carbonate or sodium bicarbonate in an aqueous solution can be used as a solution of alkali metal carbonate or alkali metal bicarbonate.
For example, water-soluble salts of inorganic or organic acids can be used as iron (III) salts. Iron (III) chloride is preferred.
The preparation of β-iron hydroxide (akaganite) is in principle known in the prior art and literature, for example U. Schwertmann and RM Cornell, “Iron Oxides in the Laboratory”, VCH Verlagsgesellschaft mbH, 1991, 95- 100. For economic reasons, in order to industrially produce adsorbents containing β-iron hydroxide, it is necessary to precipitate iron quantitatively at high pH values. As described on page 100 of the above-mentioned document, ferrihydrite also precipitates simultaneously. Mixtures of β-iron hydroxide and query hydrite such as these can also be used as adsorbents according to the invention and therefore the invention also relates to these compounds.
One or more carbohydrates and / or humic acids are added to the suspension obtained as described above. Preferably, a water soluble compound is used. Carbohydrates and / or humic acids can be added in solid form. In this case, these substances can be dissolved in the water present. However, an aqueous carbohydrate solution can also be added.
The amount of carbohydrate or humic acid is preferably selected to add at least 0.5 g of carbohydrate or humic acid per gram of iron (calculated as Fe). The maximum iron content should be 40% by weight. There is no limit on the maximum content of carbohydrates and / or humic acids and is mainly determined by economic reasons.
In particular, various sugars such as agarose, dextran, dextrin, dextran derivatives, cellulose and cellulose derivatives, soluble carbohydrates such as saccharose, maltose, lactose or mannitol can be used as carbohydrates.
Adsorbent materials containing insoluble stabilized polynuclear beta-iron hydroxides produced by the present invention, in addition to their high phosphate binding capacity, these materials are inexpensive with little release of iron. It has the advantage of being manufactured.
It is advantageous and preferred to add one or more calcium salts to the adsorbent according to the invention. Examples of suitable calcium salts include salts of inorganic or organic acids, especially calcium acetate. Phosphate binding capacity is increased by the addition of calcium salts, especially at high pH values. Adsorbents such as these adsorbents with calcium salts can be used advantageously, especially at pH values higher than 5, since sufficient phosphate binding capacity is still retained at high pH.
The addition of calcium salts, especially 400 mg to 2 g, for example about 1 g, of calcium acetate per gram of iron has been shown to be particularly advantageous.
The adsorbent according to the invention can be formulated, for example, for oral application. These adsorbents can be formulated per se or together with conventional pharmaceutical additives such as conventional carriers or auxiliary substances. For example, encapsulation can be performed using a conventional medium used in the pharmaceutical field as an encapsulation medium. The adsorbent can also be provided as granules, tablets, dragees, or included in sachets, optionally with auxiliary substances and additives. The daily dose of the adsorbent according to the invention is, for example, 1 to 3 g of iron, preferably 1.5 g.
The adsorbent according to the invention is also suitable for use in the adsorption of phosphate bound to food. For this purpose, for example, an adsorbent is mixed with the food. A prescription for this purpose can be produced, for example, as described above for the drug.
The invention is illustrated in more detail by the following examples.
Example 1
275 g of iron (III) chloride solution (d 20 = 1.098 g / ml) was added dropwise to 241.5 g of soda solution (d 20 = 1.185 g / ml) with stirring (blade stirrer) over 30 minutes. The suspension was left for 2 hours. During this time it was stirred 6 times for 10 minutes. The suspension thus obtained was treated with 300 ml of water with stirring and left for 1 hour, and the supernatant was removed by decantation. This operation was repeated 5 times.
208.3 g of a suspension having an iron content of 4.8% (measured complexometrically) were obtained.
15 g sucrose and 15 g starch were added to 208.3 g of the above suspension. The suspension was then concentrated at 50 ° C. in a rotary evaporator and dried at 40 ° C. under high vacuum.
47.2 g of a powder having an iron content of 21.2% (measured complexometrically) was obtained.
Example 2
Determination of the binding capacity of the substance prepared according to Example 1 to inorganic phosphate from aqueous phosphate solution 10 ml of sodium phosphate solution (Na 3 PO 4 × 12H 2 O 13.68 g / L) were prepared according to Example 1. To the resulting material 236 mg (corresponding to 0.9 mmol iron) (Fe: P molar ratio = 1: 0.4). After adjusting the pH to 3.0, 5.5 or 8.0, the suspension was reacted at 37 ° C. for 2 hours. Thereafter, the suspension was centrifuged and the supernatant was removed by decantation. The sample was made up to 25 ml with distilled water and its phosphorus content was measured photometrically by the phosphorus-molybdenum test.
Example 3
Except for adding 10 ml of sodium phosphate solution containing 27.36 g / L of Na 3 PO 4 × 12H 2 O to 236 mg of the substance described above (Fe: P molar ratio = 1: 0.8), the same as in Example 2, The binding ability of the material produced by Example 1 to inorganic phosphate from an aqueous phosphate solution was measured.
Example 4
Determination of the binding capacity of the substance prepared according to Example 1 to an organophosphate from an aqueous phosphate solution 10 ml of glycerophosphate solution (glycerophosphate disodium salt pentahydrate 11.02 g / L) are obtained according to Example 1. It was added to the material 236 mg (corresponding to 0.9 mmol iron) (Fe: P molar ratio = 1: 0.4). After adjusting the pH to 3.0, 5.5 or 8.0, the suspension was reacted at 37 ° C. for 2 hours. Thereafter, the suspension was centrifuged and the supernatant was removed by decantation. The sample was made up to 25 ml with distilled water and the phosphorus content was determined gravimetrically after digesting the organically bound phosphate by Lorenz reagent and precipitating the inorganic phosphate.
Example 5
Determination of the binding capacity of the substance prepared according to Example 1 to organophosphate from an aqueous phosphate solution 10 ml of phytic acid solution (23.4 g / l phytic acid) were added to 236 mg of substance prepared according to Example 1 (Corresponding to mmol) (Fe: P molar ratio = 1: 0.4). After adjusting the pH to 3.0, 5.5 or 8.0, the suspension was reacted at 37 ° C. for 2 hours. Thereafter, the suspension was centrifuged and the supernatant was removed by decanting. The sample was made up to 25 ml with distilled water and its phosphorus content was determined gravimetrically after digesting the organically bound phosphate by Lorenz reagent and precipitating the inorganic phosphate.
Example 6
30.0 g of saccharose was added to 208.3 g of the suspension prepared according to Example 1. The suspension was then concentrated at 50 ° C. in a rotary evaporator and dried at 40 ° C. under high vacuum. The phosphate binding ability of the obtained substance was measured in the same manner as in Example 2.
Example 7
30.0 g of amylopectin was added to 208.3 g of the suspension prepared according to Example 1. The suspension was then concentrated at 50 ° C. in a rotary evaporator and dried at 40 ° C. under high vacuum. The phosphate binding ability of the obtained substance was measured in the same manner as in Example 2.
Example 8
30.0 g of white dextrin (Amilum, supplied by Blattmann) was added to 208.3 g of the suspension prepared according to Example 1. The suspension was then concentrated at 50 ° C. in a rotary evaporator and dried at 40 ° C. under high vacuum. The phosphate binding ability of the obtained substance was measured in the same manner as in Example 2.
Example 9
30.0 g of humic acid (Fluka, Item No. 53860) was added to 208.3 g of the suspension prepared according to Example 1. The suspension was then concentrated at 50 ° C. in a rotary evaporator and dried at 40 ° C. under high vacuum. The phosphate binding ability of the obtained substance was measured in the same manner as in Example 2.
Example 10
Determination of binding capacity of commercially available iron (III) oxide to inorganic phosphate from aqueous phosphate solution 10 ml of sodium phosphate solution (Na 3 PO 4 × 12H 2 O 13.68 g / L) To the amount of iron (III) oxide corresponding to 0.9 mmol of iron (Fe: P molar ratio = 1: 0.4). After adjusting the pH to 3.0, 5.5 or 8.0, the suspension was reacted at 37 ° C. for 2 hours. Thereafter, the suspension was centrifuged and the supernatant was removed by decantation. The sample was made up to 25 ml with distilled water and its phosphorus content was measured photometrically by the phosphorus-molybdenum test.
Example 11
Measurement of the binding ability of α-, β- and γ-iron oxyhydroxides to inorganic phosphate from aqueous phosphate solutions. The phosphate binding ability was measured in the same manner as in Example 10.
Example 12
Measurement of the binding capacity of stabilized α-, β- and γ-iron oxyhydroxides to inorganic phosphate from aqueous phosphate solutions. In a 1: 1.5: 1.5 weight ratio of Fe: saccharose: starch, sucrose and starch were added to the iron oxyhydroxide from Example 11.
Phosphate binding ability was measured as in Example 10.
Example 13
Measurement of the binding capacity of a mixture of calcium acetate to inorganic phosphate from an aqueous phosphate solution and the substance prepared according to Example 1 0.96 g of calcium acetate (content 93.5-94.5%) containing 20.4% iron A quantity of 5 g of the material prepared according to Example 1 was added and mixed thoroughly. The phosphate binding ability of the obtained substance was measured in the same manner as in Example 2.
Example 15
The material prepared by Example 6 was suspended in water, stirred for 30 minutes, centrifuged and the upper phase was removed by decantation. This is repeated until sugar is no longer detected in the aqueous phase. In this way, after the washing operation, 1.8% of the sucrose used can still be detected in the preparation. This corresponds to 15: 1 Fe: saccharose in the washed material. This indicates that the sugar is not bound as a complex.
Example 16
In order to produce a standard rat trough with a total phosphorus content of 0.8%, the separated components of the dried powder were vigorously mixed thoroughly and then placed in a cylinder and compressed to obtain a pellet. The composition of the trough by Weender analysis corresponds to the values shown in the table below. The total phosphorus content was distributed as 0.75% organically bound phosphate and 0.05% inorganic phosphate.
In parallel with this production, a second batch of the same starting material was produced with the same formulation. This batch additionally contains 3 w / w% of the material produced according to Example 1.
After completion of production and after a storage period of about 2 months, analysis for effective phosphate was performed on both food batches. In a comparative control consisting of a formulation containing no phosphate adsorbent, a phosphate content of 0.68% was found, corresponding to 84.5% of the amount used. In the test formulation, a phosphate content of 0.50% was found, corresponding to 62.6% of the amount used.
A difference of 21.9% corresponding to P 1.75 mg / g of bulk corresponds to a binding capacity of P 1.9 mmol / g adsorbent at an adsorbent content of 3%.
Results of Weender food analysis for a control formulation containing no adsorbent:
Crude protein 19.7%
Crude fat 3.2%
Crude fiber 5.4%
Crude ash 6.5%
Water 10.9%
N 54.3% that can be poured freely
Ca content 1.2%
P content 0.8%
Kahl pellet hardness 17.3
Claims (18)
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
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DE19547356A DE19547356A1 (en) | 1995-12-19 | 1995-12-19 | Adsorbent for phosphate from aqueous medium, its preparation and use |
DE19547356.6 | 1995-12-19 | ||
PCT/EP1996/005695 WO1997022266A1 (en) | 1995-12-19 | 1996-12-19 | Adsorbent for phosphate from an aqueous medium, production and use of said adsorbent |
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JP2000506372A JP2000506372A (en) | 2000-05-30 |
JP3665345B2 true JP3665345B2 (en) | 2005-06-29 |
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JP52250797A Expired - Lifetime JP3665345B2 (en) | 1995-12-19 | 1996-12-19 | Adsorbents for phosphates from aqueous media, their manufacture and use |
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DE (2) | DE19547356A1 (en) |
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